Flame retardant copolyester compositions

ABSTRACT

The present invention relates to the combination of halogen-free flame retardant additives in a copolyester to improve the flame retardant properties of the copolyester composition while retaining clarity and impact properties, methods of making the copolyester composition and articles made from the copolyester composition. More specifically, the present invention relates to the use of a polymeric sulfonyl and phosphonate containing flame retardant compound in copolyester compositions to improve the flame retardant properties while retaining clarity, glass transition temperature, impact properties, methods of making said copolyester compositions and articles therefrom.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation from U.S. application Ser. No.14/962252, now U.S. Publication Number 2016-0168374, which claimspriority to U.S. Provisional Application No. 62/090,964 filed Dec. 12,2014, now expired, the disclosures of which are incorporated herein byreference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to the use of a combination ofhalogen-free flame retardant additives in a copolyester to improve theflame retardant properties of the copolyester composition whileretaining impact properties. More specifically, the present inventionrelates to the use of a polymeric sulfur and phosphorous containingflame retardant in copolyesters to improve the flame retardantproperties while retaining impact, glass transition temperature, andclarity properties.

Background

Flame retardant materials are added to some polymers to improve flameresistance, particularly to meet specific fire standards such as UL94V-0. However, the addition of flame retardant materials in amountsufficient to meet the fire standards may have a deleterious effect onimpact resistance, glass transition temperature, and clarity of thecopolyester film or sheet containing an effective amount of the flameretardant materials.

Copolyesters can be flame retarded in a variety of means but thesemethods have some drawbacks. Halogen compounds such as Declorane Plus,decabromodiphenyl oxide or decabromodiphenyl ether can be effectiveflame retardants, but are objectionable in the marketplace due to fearsof smoke toxicity during combustion, the formation of dioxin-typecompounds during combustion or bio-accumulation. Liquid phosphorouscompounds such as triphenyl phosphite or triphenyl phosphate can flameretard copolyesters but at effective use levels, they plasticize andsoften the copolyester thus reducing heat resistance to distortion.Solid flame retardants in the melamine and phosphorous classes can beused individually as well, but in the past, the concentrations needed toachieve flame retardancy have made the copolyester brittle or reducedtensile strength properties. Plastics used in many applications such aslighting diffusers, light emitting diode (LED) light fixtures,electronics applications, wall protection products and housings forhandheld and stationary appliances all have flammability requirementsspecified in various codes or standards. These applications also havedurability or physical property requirements in addition to flammabilityrequirements. Additionally, some building and construction and applianceapplications have banned the use of halogen containing compounds.Consequently, there is a need for copolyesters used in theseapplications that retain physical properties, are clear and usenon-halogen flame retardants.

There exists a need for an improved copolyester composition comprisingnon-halogen flame retardants and film or sheets which exhibit good flameresistance, good clarity and impact resistance.

BRIEF SUMMARY OF THE INVENTION

Applicants have unexpectedly discovered an improved copolyestercomposition comprising an effective amount of non-halogen flameretardants useful for making articles such as films, sheets, or profileswhich exhibit good flame resistance and good clarity while maintainingglass transition temperature and impact resistance.

In one aspect the present invention comprises a copolyester compositioncomprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid, from 0            to 30 mole % residues of a modifying aromatic diacid having            from 8 to 12 carbon atoms, and from 0 to 10 mole % residues            of an aliphatic dicarboxylic acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and from            35 to 99 mole % of a modifying glycol having 2 to 20 carbon            atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer comprising a sulfonyl moiety and a phenyl    phosphonate_moiety,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect the present invention comprises a copolyester compositioncomprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer comprising a sulfonyl moiety and a phenyl    phosphonate_moiety,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 23        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect the present invention comprises an article comprising, acopolyester composition comprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising    a_polymer comprising a sulfonyl moiety and a phenyl    phosphonate_moiety,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the weight % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In another aspect the present invention comprises a method of making acopolyester composition, the method comprising blending

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;    -   (b) from about 2 to about 10 wt % of a flame retardant        comprising a_polymer comprising a sulfonyl moiety and a phenyl        phosphonate moiety,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the weight % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect the present invention comprises a copolyester compositioncomprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising    a_polymer comprising polysulfonyldiphenylene phenyl phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the weight % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect the present invention comprises an article comprising, acopolyester composition comprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer comprising polysulfonyldiphenylene phenyl phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In another aspect the present invention comprises a film comprising acopolyester composition comprising:

-   (a) from greater than about 90 to about 98 wt % of the copolyester    comprising    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 4 to about 10 wt % of a flame retardant comprising a    polymer comprising a sulfonyl moiety and a phenyl phosphonate    moiety,    -   wherein the film has a thickness of 1-10 mils and has a VTM-0 or        VTM-2 rating wherein the film has less than about 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In another aspect the present invention comprises a method of making acopolyester composition, the method comprising blending

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising    a_polymer comprising polysulfonyldiphenylene phenyl phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 31 mole% 1,4-cyclohexanedimethanol and 69 mole % ethylene glycol wherein thetotal mole % of the dicarboxylic acid component is 100 mole %, the totalmole % of the glycol component is 100 mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 3.5 mole% 1,4-cyclohexanedimethanol and 96.5 mole % ethylene glycol wherein thetotal mole % of the dicarboxylic acid component is 100 mole %, the totalmole % of the glycol component is 100 mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 12 mole% 1,4-cyclohexanedimethanol and 88 mole % ethylene glycol wherein thetotal mole % of the dicarboxylic acid component is 100 mole %, the totalmole % of the glycol component is 100 mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 20 mole% 1,4-cyclohexanedimethanol and 80 mole % ethylene glycol and 0.1 mole %trimellitic anhydride wherein the total mole % of the dicarboxylic acidcomponent is 100 mole %, the total mole % of the glycol component is 100mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 50 mole% 1,4-cyclohexanedimethanol and 50 mole % ethylene glycol wherein thetotal mole % of the dicarboxylic acid component is 100 mole %, the totalmole % of the glycol component is 100 mole %.

In one aspect, the copolyester comprises a diacid component comprising100 mole % terephthalic acid, and a glycol component comprising 62.5mole % 1,4-cyclohexanedimethanol and 37.5 mole % ethylene glycol whereinthe total mole % of the dicarboxylic acid component is 100 mole %, thetotal mole % of the glycol component is 100 mole %.

In one aspect the invention comprises a copolyester compositionconcentrate comprising the copolyester and a flame retardant comprisinga polymer comprising a sulfonyl moiety and a phenyl phosphonate moiety,wherein the concentrate comprises greater than 15 wt % of the flameretardant based on the total weight of the concentrate.

In one aspect the invention comprises an article comprising any of thecopolyester compositions described above.

In one aspect the invention comprises an article comprising any of thecopolyester compositions described above wherein the article is producedby extrusion, injection molding or calendering.

In one aspect the invention comprises a film, sheet or profilecomprising any of the copolyester compositions described above.

DETAILED DESCRIPTION

The present invention may be understood more readily by reference to thefollowing detailed description of certain embodiments of the inventionand the working examples.

In accordance with the purpose(s) of this invention, certain embodimentsof the invention are described in the Summary of the Invention and arefurther described herein below. Also, other embodiments of the inventionare described herein.

The present invention provides a copolyester composition comprising acopolyester and a polymeric flame retardant having both a sulfonylmoiety and a phenyl phosphonate moiety in which the copolyestercomposition exhibits good flame retardancy, clarity and good punctureresistance, articles made therefrom, and methods of making thecomposition and articles. The present invention involves the use of ahalogen-free flame retardant additive to improve the flame retardantproperties while retaining impact and clarity properties. The flameretardant additive is a sulfur and phosphorous-containing polymericcompound. When the flame retardant is added at the appropriateconcentration with a copolyester, a flame retarded composition whichretains ductile instrumented impact properties (ASTM D3763) whileachieving a UL94 V-0 rating and good clarity with low haze according toASTM D1003.

In one aspect the present invention comprises a copolyester compositioncomprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer consisting essentially of polysulfonyldiphenylene phenyl    phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In one aspect the present invention comprises an article comprising, acopolyester composition comprising:

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer consisting essentially of polysulfonyldiphenylene phenyl    phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

In another aspect the present invention comprises a method of making acopolyester composition, the method comprising blending

-   (a) from greater than 90 to about 98 wt % of the copolyester, the    copolyester comprising:    -   (i) a diacid component comprising        -   from 70 to 100 mole % residues of terephthalic acid,        -   from 0 to 30 mole % residues of a modifying aromatic diacid            having from 8 to 12 carbon atoms, and        -   from 0 to 10 mole % residues of an aliphatic dicarboxylic            acid; and    -   (ii) a glycol component comprising        -   from 1 to 65 mole % cyclohexanedimethanol residues and        -   from 35 to 99 mole % of a modifying glycol having 2 to 20            carbon atoms;-   (b) from about 2 to about 10 wt % of a flame retardant comprising a    polymer consisting essentially of polysulfonyldiphenylene phenyl    phosphonate,    -   wherein the copolyester composition has a UL 94 V-0 rating,    -   wherein the energy at maximum load is greater than about 15        Joules measured on a 100 mm×100 mm×1.5 mm plaque according to        ASTM D3763;    -   wherein the copolyester composition has about less than 10% haze        according to ASTM D1003,    -   wherein the wt % is based on the weight of the copolyester,        wherein the total mole % of the dicarboxylic acid component is        100 mole % and the total mole % of the glycol component is 100        mole %.

Copolyesters useful in the present invention comprise residues of anaromatic diacid and residues of two or more glycols.

The term “copolyester,” as used herein, is intended to include“polyesters” and is understood to mean a synthetic polymer prepared bythe reaction of one or more difunctional carboxylic acids and/ormultifunctional carboxylic acids with one or more difunctional hydroxylcompounds and/or multifunctional hydroxyl compounds. Typically thedifunctional carboxylic acid can be a dicarboxylic acid and thedifunctional hydroxyl compound can be a dihydric alcohol such as, forexample, glycols. Furthermore, as used in this application, theinterchangeable terms “diacid” or “dicarboxylic acid” includemultifunctional acids, such as branching agents. The term “glycol” asused in this application includes, but is not limited to, diols,glycols, and/or multifunctional hydroxyl compounds. Alternatively, thedifunctional carboxylic acid may be a hydroxy carboxylic acid such as,for example, p-hydroxybenzoic acid, and the difunctional hydroxylcompound may be an aromatic nucleus bearing 2 hydroxyl substituents suchas, for example, hydroquinone. The term “residue,” as used herein, meansany organic structure incorporated into a polymer through apolycondensation and/or an esterification reaction from thecorresponding monomer. The term “repeating unit,” as used herein, meansan organic structure having a dicarboxylic acid residue and a diolresidue bonded through a carbonyloxy group. Thus, for example, thedicarboxylic acid residues may be derived from a dicarboxylic acidmonomer or its associated acid halides, esters, salts, anhydrides, ormixtures thereof. As used herein, therefore, the term dicarboxylic acidis intended to include dicarboxylic acids and any derivative of adicarboxylic acid, including its associated acid halides, esters,half-esters, salts, half-salts, anhydrides, mixed anhydrides, ormixtures thereof, useful in a reaction process with a diol to makepolyester. As used herein, the term “terephthalic acid” is intended toinclude terephthalic acid itself and residues thereof as well as anyderivative of terephthalic acid, including its associated acid halides,esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, ormixtures thereof or residues thereof useful in a reaction process with adiol to make polyester. The term “modifying aromatic diacid” means anaromatic dicarboxylic acid other the terephthalic acid. The term“modifying glycol” means a glycol other than 1,4-cyclohexane dimethanol.

In one embodiment, terephthalic acid may be used as the startingmaterial. In another embodiment, dimethyl terephthalate may be used asthe starting material. In another embodiment, mixtures of terephthalicacid and dimethyl terephthalate may be used as the starting materialand/or as an intermediate material.

The copolyesters used in the present invention typically can be preparedfrom dicarboxylic acids and dials which react in substantially equalproportions and are incorporated into the copolyester polymer as theircorresponding residues. The copolyesters of the present invention,therefore, can contain substantially equal molar proportions of acidresidues (100 mole %) and diol (and/or multifunctional hydroxylcompounds) residues (100 mole %) such that the total moles of repeatingunits is equal to 100 mole %. The mole percentages provided in thepresent disclosure, therefore, may be based on the total moles of acidresidues, the total moles of diol residues, or the total moles ofrepeating units. For example, a copolyester containing 30 mole %isophthalic acid, based on the total acid residues, means thecopolyester contains 30 mole % isophthalic acid residues out of a totalof 100 mole % acid residues. Thus, there are 30 moles of isophthalicacid residues among every 100 moles of acid residues. In anotherexample, a copolyester containing 30 mole % 1,4-cyclohexanedimethanol,based on the total diol residues, means the copolyester contains 30 mole% 1,4-cyclohexanedimethanol residues out of a total of 100 mole % diolresidues. Thus, there are 30 moles of 1,4-cyclohexanedimethanol residuesamong every 100 moles of diol residues.

The copolyesters comprise 70 to 100 mole % of an aromatic diacid. In oneembodiment, the copolyesters comprise 70 to 100 mole % of terephthalicacid (TPA). Alternatively, the copolyesters comprise 80 to 100 mole %TPA, or 90 to 100 mole % TPA or 95 to 100 mole % TPA or 100 mole % TPA.For the purposes of this disclosure, the terms “terephthalic acid” and“dimethyl terephthalate” are used interchangeably herein.

In addition to terephthalic acid, the dicarboxylic acid component of thecopolyester useful in the invention can comprise up to 30 mole %, up to20 mole %, up to 10 mole %, up to 5 mole %, or up to 1 mole % of one ormore modifying aromatic dicarboxylic acids. Yet another embodimentcontains 0 mole % modifying aromatic dicarboxylic acids. Thus, ifpresent, it is contemplated that the amount of one or more modifyingaromatic dicarboxylic acids can range from any of these precedingendpoint values including, for example, from 0.01 to 30 mole %, 0.01 to20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01to 1 mole. In one embodiment, modifying aromatic dicarboxylic acids thatmay be used in the present invention include but are not limited tothose having up to 20 carbon atoms, and which can be linear,para-oriented, or symmetrical. Examples of modifying aromaticdicarboxylic acids which may be used in this invention include, but arenot limited to, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-,1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, andtrans-4,4′-stilbenedicarboxylic acid, and esters thereof. In oneembodiment, the modifying aromatic dicarboxylic acid is isophthalicacid.

The carboxylic acid component of the copolyesters useful in theinvention can be further modified with up to 10 mole %, such as up to 5mole % or up to 1 mole % of one or more aliphatic dicarboxylic acidscontaining 2-16 carbon atoms, such as, for example, malonic, succinic,glutaric, adipic, pimelic, suberic, azelaic and dodecanedioicdicarboxylic acids. Certain embodiments can also comprise 0.01 or moremole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %,or 10 or more mole % of one or more modifying aliphatic dicarboxylicacids. Yet another embodiment contains 0 mole % modifying aliphaticdicarboxylic acids. Thus, if present, it is contemplated that the amountof one or more modifying aliphatic dicarboxylic acids can range from anyof these preceding endpoint values including, for example, from 0.01 to10 mole % and from 0.1 to 10 mole %. The total mole % of thedicarboxylic acid component is 100 mole %.

Esters of terephthalic acid and the other modifying dicarboxylic acidsor their corresponding esters and/or salts may be used instead of thedicarboxylic acids. Suitable examples of dicarboxylic acid estersinclude, but are not limited to, the dimethyl, diethyl, dipropyl,diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the estersare chosen from at least one of the following: methyl, ethyl, propyl,isopropyl, and phenyl esters.

The copolyesters useful in the copolyesters compositions of theinvention can comprise from 0 to 10 mole %, for example, from 0.01 to 5mole %, from 0.01 to 1 mole %, from 0.05 to 5 mole %, from 0.05 to 1mole %, or from 0.1 to 0.7 mole %, based the total mole percentages ofeither the diol or diacid residues; respectively, of one or moreresidues of a branching monomer, also referred to herein as a branchingagent, having 3 or more carboxyl substituents, hydroxyl substituents, ora combination thereof. In certain embodiments, the branching monomer oragent may be added prior to and/or during and/or after thepolymerization of the polyester. The copolyester(s) useful in theinvention can thus be linear or branched.

Examples of branching monomers include, but are not limited to,multifunctional acids or multifunctional alcohols such as trimelliticacid, trimellitic anhydride, pyromellitic dianhydride,trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaricacid, 3-hydroxyglutaric acid and the like. In one embodiment, thebranching monomer residues can comprise 0.1 to 0.7 mole % of one or moreresidues chosen from at least one of the following: trimelliticanhydride, pyromellitic dianhydride, glycerol, sorbitol,1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimericacid. The branching monomer may be added to the polyester reactionmixture or blended with the polyester in the form of a concentrate asdescribed, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, whosedisclosure regarding branching monomers is incorporated herein byreference.

All of the following embodiments of copolyesters are useful in all ofthe embodiments of the present invention. In certain embodiments theglycol component of the copolyester comprises ethylene glycol and1,4-cyclohexanedimethanol. In one embodiment the glycol component of thecopolyester comprises 1 to 65 mole % 1,4-cyclohexanedimethanol and 35 to99 mole % ethylene glycol. In one embodiment the glycol component of thecopolyester comprises 1 to 50 mole % 1,4-cyclohexanedimethanol and 50 to99 mole % ethylene glycol. In one embodiment the glycol component of thecopolyester comprises about 1 to 31 mole % 1.4-cyclohexanedimethanol andabout 69 to 99 mole % ethylene glycol. In one embodiment the glycolcomponent of the copolyester comprises about 31 mole %1,4-cyclohexanedimethanol and about 69 mole % ethylene glycol. In oneembodiment the glycol component of the copolyester comprises about 5 to65 mole % 1,4-cyclohexanedimethanol and about 35 to 95 mole % ethyleneglycol. In one embodiment the glycol component of the copolyestercomprises about 5 to 50 mole % 1,4-cyclohexanedimethanol and about 50 to95 mole % ethylene glycol. In one embodiment the glycol component of thecopolyester comprises about 10 to 65 mole % 1,4-cyclohexanedimethanoland about 35 to 90 mole % ethylene glycol. In one embodiment the glycolcomponent of the copolyester comprises about 10 to 50 mole %1,4-cyclohexanedimethanol and about 50 to 90 mole % ethylene glycol. Inone embodiment the glycol component of the copolyester comprises about20 to 65 mole % 1,4-cyclohexanedimethanol and about 35 to 80 mole %ethylene glycol. In one embodiment the glycol component of thecopolyester comprises about 20 to 50 mole % 1,4-cyclohexanedimethanoland about 50 to 80 mole % ethylene glycol. In one embodiment the glycolcomponent of the copolyester comprises about 30 to 65 mole %1,4-cyclohexanedimethanol and about 35 to 70 mole % ethylene glycol. Inone embodiment the glycol component of the copolyester comprises about30 to 50 mole % 1,4-cyclohexanedimethanol and about 50 to 70 mole %ethylene glycol.

The 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof,for example a cis/trans ratio of 60:40 to 40:60. In another embodiment,the trans-1,4-cyclohexanedimethanol can be present in an amount of 60 to80 mole %. Alternatively, 1,2- and/or 1-3-cyclohexanedimethanol may beused individually or in combination with each other and/or1,4-cyclohexanedimethanol.

The glycol component of the copolyester portion of the copolyestercomposition useful in all of the embodiments of the invention cancontain 25 mole % or less of one or more modifying glycols which are notethylene glycol or 1,4-cyclohexanedimethanol; in one embodiment, thecopolyesters useful in the invention may contain less than 15 mole % ofone or more modifying glycols. In another embodiment, the copolyestersuseful in the invention can contain 10 mole % or less of one or moremodifying glycols. In another embodiment, the copolyesters useful in theinvention can contain 5 mole % or less of one or more modifying glycols.In another embodiment, the copolyesters useful in the invention cancontain 3 mole % or less of one or more modifying glycols. In anotherembodiment, the copolyesters useful in the invention can contain 0 mole% modifying glycols. Certain embodiments can also contain 0.01 or moremole %, such as 0.1 or more mole %, 1 or more mole %, 5 or more mole %,or 10 or more mole % of one or more modifying glycols. Thus, if present,it is contemplated that the amount of one or more modifying glycols canrange from any of these preceding endpoint values including, forexample, from 0.01 to 15 mole % and from 0.1 to 10 mole %.

Modifying glycols useful in the copolyesters useful in all embodimentsof the invention refer to diols other than ethylene glycol and1,4-cyclohexanedimethanol and may contain 2 to 16 carbon atoms. Examplesof suitable modifying glycols include, but are not limited to,1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, p-xylene glycol,2,2,4,4-tetramethylcyclobutane-1,3-diol or mixtures thereof. In anotherembodiment, the modifying glycols are 1,3-propanediol and/or1,4-butanediol.

In one aspect, the copolyester compositions of the present inventionuseful for meeting the UL 94 V-0 rating and energy at maximum load of atleast 15 Joules comprise from 2 to 10 wt % of the flame retardant. Inone aspect, the copolyester compositions of the present invention usefulfor meeting the UL 94 V-0 rating and energy at maximum load of at least23 Joules comprise from 2 to 10 wt % of the flame retardant. In oneaspect, the copolyester compositions of the present invention useful formeeting the UL 94 V-0 rating and energy at maximum load of at least 15Joules comprise from 4 to 10 wt % of the flame retardant. In one aspect,the copolyester compositions of the present invention useful for meetingthe UL 94 V-0 rating and energy at maximum load of at least 15 Joulescomprise from 2 to 8 wt % of the flame retardant. In one aspect, thecopolyester compositions of the present invention useful for meeting theUL 94 V-0 rating and energy at maximum load of at least 23 Joulescomprise from 5 to 7 wt % of the flame retardant.

In one aspect, the copolyester compositions of the present inventioncomprise a copolyester composition comprising any of the copolyestersdescribed above and the polymeric flame retardant having both a sulfonylmoiety and a phenyl phosphonate moiety and has a glass transitiontemperature (Tg) of from 70 to 90° C. The Tg of the copolyesters usefulin the invention, if measured, was determined using a TA DSC 2920 fromThermal Analyst Instrument at a scan rate of 20° C./min. Thecopolyesters of the present invention can have a Tg of 70° C. to 90° C.,70° C. to 80° C., or 80° C. to 90° C.

In one aspect, the copolyester compositions of the present inventioncomprise a copolyester composition comprising any of the copolyestersdescribed above and the polymeric flame retardant having both a sulfonylmoiety and a phenyl phosphonate moiety, and are the compositionsvisually clear. The term “visually clear” is defined herein as a lowamount of cloudiness, haziness, and/or muddiness, when inspectedvisually.

In one embodiment, molded samples of the invention can be measured foroptical (light transmission and haze) using ASTM D 1003. In oneembodiment, these measurements can be performed on samples having athickness of ⅛ inch. In another embodiment, these measurements areperformed on samples measuring 4 inches×4 inches.

The term “% haze”, as used herein, refers to haze values determinedaccording to ASTM Method D1003 using a HunterLab UltraScan Sphere 8000Colorimeter manufactured by Hunter Associates Laboratory, Inc., Reston,Va. using Hunter's Universal Software (version 3.8) (% Haze=100*DiffuseTransmission/Total Transmission). For the compositions of the invention,haze is determined by molding or casting the composition into a sheet orfilm having a thickness of ⅛ inch or less and measuring the hazeaccording to D1003 and/or the procedure described in the examples. Againin one embodiment, these measurements can be performed on samples havinga thickness of ⅛ inch. In another embodiment, these measurements areperformed on samples measuring 4 inches×4 inches.

In one aspect of the invention, each embodiment of the invention canhave haze values of from 0 to 10, or 0 to 5, or 1 to 10, or 1 to 5, or 5to 10 percent as determined by ASTM Method D1003 or by any other methoddescribed herein. While these haze values can be present at any percentloading, in one embodiment, the polymer blends of the invention can havea haze value of less than 10% at up to 10% by weight of at least oneflame retardant wherein the haze value is determined by ASTM MethodD1003 or by other methods described herein and where the weightpercentage of the flame retardant is based on the total weight of thecopolyester.

In one embodiment of the invention, films having a thickness of lessthan 10 mils have haze of less than about 10%, according to ASTM D1003,while maintaining a UL-94 VTM-0 or VTM-2 rating.

Certain embodiments of the present invention comprise a copolyestercomposition comprising any of the copolyesters described above and thepolymeric flame retardant having both a sulfonyl moiety and a phenylphosphonate moiety and from 0.5 to 2.0 wt % of a drip suppressant.Certain embodiments of the present invention comprise a copolyestercomposition comprising any of the copolyesters described above and theflame retardant polysulfonyldiphenylene phenyl phosphonate and from 0.5to 2.0 wt % of a drip suppressant. The drip suppressant comprises afluoropolymer. The fluoropolymer includes, but is not limited to,Teflon™.

The copolyester compositions useful in the invention can possess one ormore of the following properties. In one embodiment, the copolyestercompositions useful in the invention exhibit, as shown by punctureresistance, a instrumented energy at maximum load of about 15 J at 23°C. with a 100 mm×100 mm×1.5 mm plaque thick bar determined according toASTM D3763; in one embodiment, the copolyester compositions useful inthe invention exhibit a instrumented energy at maximum load of at about23 J at 23° C. with a 100 mm×100 mm×1.5 mm plaque thick bar determinedaccording to ASTM D3763; the copolyester compositions useful in theinvention exhibit a instrumented energy at maximum load of at about 25 Jat 23° C. with a 100 mm×100 mm×1.5 mm plaque thick bar determinedaccording to ASTM D3763; in one embodiment, the copolyester compositionsuseful in the invention exhibit a instrumented energy at maximum load ofgreater than 33 J at 23° C. with a 100 mm×100 mm×1.5 mm plaque thick bardetermined according to ASTM D3763.

Certain embodiments of the present invention comprise an impact modifierto improve impact strength of the copolyester compositions The impactmodifiers comprise plastics and/or elastomers including, but not limitedto, Acrylonitrile Butadiene Styrene (ABS), Methyl Methacrylate ButadieneStyrene (MBS), Acrylic (Butyl Acrylate Methyl Acrylate), CopolyesterEther copolymer (COPE, Trade name ECDEL, from Eastman Chemical Company),Ethylene Methacrylate Copolymer (EMAC), Aliphatic Aromatic Copolyester(Trade name EASTAR BIO, from Eastman Chemical Company), and reactiveAcrylic (Ethylene Acrylic Ester Glycidyl Methacrylate).

The polyester portion of the copolyester compositions useful in theinvention can be made by processes known from the literature such as,for example, by processes in homogenous solution, by transesterificationprocesses in the melt, and by two phase interfacial processes. Suitablemethods include, but are not limited to, the steps of reacting one ormore dicarboxylic acids with one or more glycols at a temperature of100° C. to 315° C. at a pressure of 0.1 to 760 mm Hg for a timesufficient to form a copolyester. See U.S. Pat. No. 3,772,405 formethods of producing copolyesters, the disclosure regarding such methodsis hereby incorporated herein by reference.

In another aspect, the invention relates to films or sheets comprising acopolyester produced by a process comprising:

(I) heating a mixture comprising the monomers useful in any of thecopolyesters in the invention in the presence of a catalyst at atemperature of 150 to 240° C. for a time sufficient to produce aninitial copolyester;

(II) heating the initial copolyester of step (I) at a temperature of 240to 320° C. for 1 to 4 hours; and

(III) removing any unreacted glycols.

Suitable catalysts for use in this process include, but are not limitedto, organo-zinc or tin compounds. The use of this type of catalyst iswell known in the art. Examples of catalysts useful in the presentinvention include, but are not limited to, zinc acetate, butyltintris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide. Othercatalysts may include, but are not limited to, those based on titanium,zinc, manganese, lithium, germanium, and cobalt. Catalyst amounts canrange from 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppmor 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 basedon the catalyst metal and based on the weight of the final polymer. Theprocess can be carried out in either a batch or continuous process.

Typically, step (I) can be carried out until 50% by weight or more ofthe glycol has been reacted. Step (I) may be carried out under pressure,ranging from atmospheric pressure to 100 psig. The term “reactionproduct” as used in connection with any of the catalysts useful in theinvention refers to any product of a polycondensation or esterificationreaction with the catalyst and any of the monomers used in making thepolyester as well as the product of a polycondensation or esterificationreaction between the catalyst and any other type of additive.

Typically, step (II) and step (III) can be conducted at the same time.These steps can be carried out by methods known in the art such as byplacing the reaction mixture under a pressure ranging from 0.002 psig tobelow atmospheric pressure, or by blowing hot nitrogen gas over themixture.

In one aspect the invention comprises a copolyester compositionconcentrate comprising the copolyester and a flame retardant comprisinga polymer comprising a sulfonyl moiety and a phenyl phosphonate moiety,wherein the concentrate comprises greater than 15 wt % of the flameretardant based on the total weight of the concentrate. In one aspectthe invention comprises a copolyester composition concentrate comprisingthe copolyester and a flame retardant consisting essentially of apolymer having both a sulfonyl moiety and a phenyl phosphonate moiety,wherein the concentrate comprises greater than 15 wt % of the flameretardant based on the total weight of the concentrate. In one aspectthe invention comprises a copolyester composition concentrate comprisingthe copolyester and a flame retardant consisting essentially ofpolysulfonyldiphenylene phenyl_phosphonate, wherein the concentratecomprises greater than 15 wt % of the flame retardant based on the totalweight of the concentrate. Alternatively, the flame retardant in theconcentrate may comprise more than 20 wt % or more than 30 wt % or morethan 40 wt % or more than 50 wt % or more than 60 wt % or more than 70wt % or more than 80 wt % or more than 90 wt % of the copolyesterconcentrate based on the total weight of the concentrate.

The flame retardant can be incorporated into the copolyester in aconcentrate form by any conventional method for ultimate formation intoan article.

The flame retardant can be incorporated in a plastics compounding linesuch as a twin screw compounding line to form a copolyester compositionconcentrate. In this case copolyester pellets are dried for 4 to 6 hoursat 150° F. to 160° F. (65.6° C. to 71.1° C.) to reduce moisture. Thepellets are then fed into the throat of the extruder and melted from430° F. to 520° F. (221° C. to 271° C.) to produce a viscousthermoplastic material. Alternatively, the flame retardant ispre-blended and added as a single powder with a loss-in-weight feeder oradded singly in a loss-in-weight feeder. The rotation of the two screwsdisperses the flame retardant into the copolyester. The mixture is thenextruded through a die to produce multiple strands. In certainembodiments, the strands are fed through a water trough to cool thepellets. Upon exiting the water trough, the strands are dried and fedinto a dicer to cut the strands into pellets. Alternatively, the mixturecan be extruded through a circular flat plate die with multiple openingsinto water. The flat plate die has a rotating cutter that slices thestrands as they extrude from the die to produce pellets. The continuousflow of water cools the pellets and transports them to a drying section,typically a centrifuge to separate the pellets from the water.

Alternatively, the flame retardants are incorporated into a plasticscompounding line such as a two-rotor continuous compounding mixer (suchas a Farrell Continuous Mixer) to form a copolyester compositionconcentrate. In this case copolyester pellets are dried for 4 to 6 hoursat 150° F. to 160° F. (65.6° C. to 71.1° C.) to reduce moisture. Thecopolyester pellets and the flame retardant are fed into the throat ofthe continuous mixer and melted into a homogenous mixture at 430° F. to520° F. (221° C. to 271° C). The output rate of the mixer is controlledby varying the area of a discharge orifice. The melt can be sliced offinto ‘loaves’ and fed to a two roll mill or the throat of a single screwextruder. In the case of the melt being fed to a two-roll mill, the meltcovers one of the rolls to form a sheet of the concentrate which is cutinto strips which are fed to the throat of a single screw extruder. Themixture is then extruded through a die to produce multiple strands. Thestrands are fed through a water trough to cool the pellets. Upon exitingthe water trough, the strands are dried and fed into a dicer to cut thestrands into pellets. Alternatively, the mixture can be extruded througha circular flat plate die with multiple openings into water. The flatplate die has a rotating cutter that slices the strands as they extrudefrom the die to produce pellets. The continuous flow of water cools thepellets and transports them to a drying section, typically a centrifugeto separate the pellets from the water. In the case of the ‘loaves’(relatively large portions of the concentrate) being fed to a singlescrew extruder, the mixture is extruded through a die to producemultiple strands. The strands can be fed through a water trough to coolthe pellets. Upon exiting the water trough, the strands are dried andfed into a dicer to cut the strands into pellets. Alternatively, themixture can be extruded through a circular flat plate die with multipleopenings into water. The flat plate die has a rotating cutter thatslices the strands as they extrude from the die to produce pellets. Thecontinuous flow of water cools the pellets and transports them to adrying section, typically a centrifuge to separate the pellets from thewater.

Alternatively, the flame retardant is incorporated in a high-intensitymixer such a Banbury® batch type mixer to form a copolyester compositionconcentrate. In this case, the copolyester pellets can be dried for 4 to6 hours at 150° F. to 160° F. (65.6° C. to 71.1° C.) to reduce moisture.The copolyester pellets and the flame retardants are charged into ahigh-intensity mixer and a ram lowered to compress the pellet/flameretardants mixture into the mixing chamber. Two rotating mixer bladesmelt the pellets and disperse the flame retardant into the melt. Whenthe desired temperature is reached, a door is opened in the bottom ofthe mixer and the mixture is dropped onto a two roll mill. A ribbon fromthe two roll mill can then be fed to a single screw extruder. Themixture is then extruded through a die to produce multiple strands. Thestrands can be fed through a water trough to cool the pellets. Uponexiting the water trough, the strands are dried and fed into a dicer tocut the strands into pellets. Alternatively, the mixture can be extrudedthrough a circular flat plate die with multiple openings into water. Theflat plate die has a rotating cutter that slices the strands as theyextrude from the die to produce pellets. The continuous flow of watercools the pellets and transports them to a drying section, typically acentrifuge to separate the pellets from the water.

The present invention includes plastic articles comprising thecopolyester compositions. The plastic articles may be made by processescomprising, but not limited to, extrusion of the copolyester compositionto produce a continuous flat sheet or profile or injection molding tocreate discrete articles or calendering to produce a continuous film orsheet.

Films and/or sheets useful in the present invention can be of anythickness which would be apparent to one of ordinary skill in the art.In one embodiment, the films(s) of the invention have a thickness ofless than 30 mils or less than 20 mils or less than 10 mils or less than5 mils. In one embodiment, the sheets of the invention have a thicknessof greater than 30 mils. In one embodiment, the sheets of the inventionhave a thickness of from 30 mils to 100 mils or from 30 mils to 200 milsor from 30 mils to 500 mils.

The invention further relates to the films and/or sheets comprising thepolyester compositions of the invention. The methods of forming thepolyesters into films and/or sheets are well known in the art. Examplesof films and/or sheets of the invention include, but are not limited to,extruded films and/or sheets, calendered films and/or sheets,compression molded films and/or sheets, injection molded films orsheets, and solution casted films and/or sheets. Methods of making filmand/or sheet include but are not limited to extrusion, calendering,extrusion molding, compression molding, and solution casting. Thesefilms or sheets may be made or subjected to further processing such asorientation (uniaxial or biaxial), heat setting, surface treatment, etc.

In one embodiment of the invention comprises a flat sheet or profile.The sheet or profile is prepared by extruding the copolyestercomposition to produce a flat sheet or profile. In this case, pellets ofthe copolyester composition are dried at 150° F. to 160° F. (65.6° C. to71.1° C.) for 4 to 6 hours and are then fed to either a single screwextruder, a twin-screw extruder, or a conical twin screw extruder. Thecopolyester composition pellets are conveyed and compressed by thescrew(s) down the extruder barrel to melt the pellets and discharge themelt from the end of the extruder. The melt is fed through a screeningdevice to remove debris and/or a melt pump to reduce pressure variationscaused by the extruder. The melt is then fed through a die to create acontinuous flat sheet or into a profile die to create a continuousshape. In one embodiment of the invention comprising a flat sheet die,the melt is extruded onto a series of metal rolls, typically three, tocool the melt and impart a finish onto the sheet. The flat sheet is thenconveyed in a continuous sheet for a distance or period of timesufficient to cool the sheet. The sheet is then trimmed to the desiredwidth and then either rolled up into a roll or sheared or sawed intosheet form of desired dimensions. A flat sheet can also be formed into ashaped article through mechanical means to form a desired shaped articleand then cooled either by spraying with water, by conveying through awater trough or by blowing air on the shaped article. The article thensawed or sheared to the desired length. In the case of a profile die,the die is designed to produce the desired shape of the profile. Afterexiting the die, the profile is then cooled either by spraying withwater, by conveying through a water trough or by blowing air on theprofile. The profile is then sawed or sheared to the desired length. Inthe case of a fiber, the fiber can be pulled out of the extrusion diespinnerets to the desired fiber diameter and crystallized for physicalproperty enhancement.

Another embodiment of the invention comprises mixing neat copolyesterpellets with a concentrate of flame retardant and then extruding thecopolyester composition. The flame retardant concentrate can becompounded as a pellet. The pellets are dried at 150° F. to 160° F.(65.6° C. to 71.1° C.) for 4 to 6 hours before extrusion. The pelletsare dried after being blended in a low-intensity mixer such as a ribbonblender, a tumbler, or conical screw blender. The pellets are then fedto an extruder including, but not limited to, a single screw extruder, atwin-screw extruder, or a conical twin screw extruder. The pellets areconveyed and compressed by the screw(s) down the extruder barrel to meltthe pellets and discharge the melt from the end of the extruder. Themelt is typically fed through a screening device to remove debris and/ora melt pump to reduce pressure variations caused by the extruder. Themelt is then fed through a die to create a continuous flat sheet or intoa profile die to create a continuous shape. In the case of the flatsheet die, the melt is extruded onto a series of metal rolls, typicallythree, to cool the melt and impart a finish onto the sheet. The flatsheet is then conveyed in a continuous sheet for a distance or period oftime sufficient to cool the sheet. It can then be trimmed to the desiredwidth and then either rolled up into a roll or sheared or sawed intosheet form. A flat sheet can also be formed into a shape throughmechanical means to form a desired shape and then cooled either byspraying with water, through a water trough or by blowing air on theshaped article. It can then be sawed or sheared to the desired length.In the case of a film, the film may be produced and wound into a roll.In the case of a profile die, the die is designed to produce the desiredshape of the article. After exiting the die, the profile can then becooled either by spraying with water, through a water trough or byblowing air on the profile. It can then be sawed or sheared to thedesired length. In the case of a fiber, the fiber can be pulled out ofthe extrusion die spinnerets to the desired fiber diameter andcrystallized for physical property enhancement.

Another embodiment of the invention consists of mixing neat copolyesterpellets with a flame retardant concentrate and then extruding them witheither short or long strand glass fiber reinforcement or extruding theminto a continuous glass fiber composite film, sheet or tape. The flameretardant can be compounded as a single pellet. The pellets are dried at150° F. to 160° F. (65.6° C. to 71.1° C.) for 4 to 6 hours beforeextrusions. The pellets can be dried separately or together after beingblended in a low-intensity mixer such as a ribbon blender, a tumbler, orconical screw blender. The pellets are then fed to either a single screwextruder, a twin-screw extruder, or a conical twin screw extruder. Thepellets are conveyed and compressed by the screw(s) down the extruderbarrel to melt the pellets and discharge the melt from the end of theextruder. The melt can be fed through a screening device to removedebris and/or a melt pump to reduce pressure variations caused by theextruder. The melt can then be fed through a die to create a continuousflat sheet or into a profile die to create a continuous shape. In thecase of the flat sheet die, the melt is extruded onto a series of metalrolls, typically three, to cool the melt and impart a finish onto thesheet. The flat sheet is then conveyed in a continuous sheet to cool thesheet. It can then be trimmed to the desired width and then eitherrolled up into a roll or sheared or sawed into sheet form. A flat sheetcan also be formed into a shape through mechanical means to form adesired shape and then cooled either by spraying with water, through awater trough or by blowing air on the profile. It can then be sawed orsheared to the desired length or a film may be produced and wound into aroll. In the case of a profile die, the die is designed to produce thedesired shape of the article. After exiting the die, it can then becooled either by spraying with water, through a water trough or byblowing air on the profile. It can then be sawed or sheared to thedesired length. In the case of a fiber, the fiber can be pulled out ofthe extrusion die spinnerets to the desired fiber diameter andcrystallized for physical property enhancement.

Another embodiment of the invention comprises extruding fully compoundedpellets of the copolyester composition, comprising the copolyester andflame retardants, to produce an injection molded article. In this case,the pellets are dried at 150° F. to 160° F. (65.6° C. to 71.1° C.) for 4to 6 hours to dry the pellets which are then fed to a reciprocatingsingle screw extruder. The pellets are melted by the screw rotation andreciprocating action. Once the pellets reach the desired temperature, agate is opened at the end of the extruder and the melted plastic ispumped by the screw into a heated mold to form an article of the desiredshape. Once the mold is filled, a coolant is pumped through the mold tocool it and the melted plastic. Once the plastic has solidified, themold is opened and the article is removed from the mold.

Another embodiment of the invention comprises mixing neat copolyesterpellets with a concentrate of the flame retardant to form thecopolyester composition and then extruding the copolyester compositionto produce an injection molded article with or without short or longstrand glass fiber reinforcement. The pellets are dried at 150° F. to160° F. (65.6° C. to 71.1° C.) for 4 to 6 hours and are then fed to areciprocating single screw extruder. The pellets can be dried separatelyor together after being blended in a low-intensity mixer including, butnot limited to, a ribbon blender, a tumbler, or conical screw blender.Once the pellets reach the desired temperature, a gate is opened at theend of the extruder and the melted plastic is pumped by the screw into aheated mold to form an article of the desired shape. Once the mold isfilled, a coolant is pumped through the mold to cool it and the meltedplastic. Once the plastic has solidified, the mold is opened and thearticle is removed from the mold.

Another embodiment of the invention comprises mixing neat copolyesterpellets with a concentrate of flame retardants to form the copolyestercomposition and then calendering the copolyester composition to producea film product. Calendering is a well-known process of forming a film orsheet through successive co-rotating parallel rollers. In thecalendering process, the pellets do not need to be pre-dried as theprocessing temperatures are low enough (350° F. to 400° F.; 177° C. to204° C.) so degradation and hydrolysis of the polyester does not occurin a significant amount. The copolyester and flame retardant compositionmay be melted by using a high intensity mixer or extruder, including butnot limited to, Buss Ko-kneader, a planetary gear extruder, Farrellcontinuous mixer, a twin screw extruder, or a Banbury® type mixer. Themelt is then conveyed to the calender. A calender typically consistsessentially of a system of three or more large diameter heated rollerswhich convert high viscosity plastic into a film or sheet. The flatsheet or film is conveyed in a continuous web to cool the sheet. It canthen be trimmed to the desired width and then either rolled up into aroll or sheared or sawed into sheet form.

Although the copolyester composition may be prepared by mixing orblending a concentrate of flame retardants and copolyester, thecopolyester composition may alternatively be prepared by blending theflame retardants directly with the copolyester, using any of the mixingor blending processed previously described for making the copolyestercomposition by blending the flame retardant concentrate and thecopolyester. The two flame retardants may be mixed or blended with thecopolyester simultaneously or sequentially.

This invention can be further illustrated by the following examples ofpreferred embodiments thereof, although it will be understood that theseexamples are included merely for purposes of illustration and are notintended to limit the scope of the invention unless otherwisespecifically indicated.

EXAMPLES

The following abbreviations are used: kN is kiloNewtons; J is Joules; %NB is percent no break; J/m is Joules per meter; LOI is Loss OnIgnition; wt % is weight percent; TGA is thermographic analysis; TPA isterephthalic acid; and 1,4-CHDM is 1,4-cyclohexanedimethanol. PETG is aglycol modified polyethylene terephthalate. The PETG used in theexamples is copolyester A, copolyester B and copolyester C with thecompositions shown in Table 1. Samples were prepared similarly by mixingthe copolyester A, B, or C and the flame retardant in a 30 mm twin screwcompounding extruder at approximately 450° F. to make pellets of eachformulation. Samples of each formulation were then injection molded toproduce test samples for flammability, tensile properties, instrumentedimpact, limiting oxygen index and thermal gravimetric analysis. Sheetsamples were prepared for the ASTM E84 by mixing pellets of copolyesterA, B or C and flame retardant concentrates and extruding sheet on anextrusion line at approximately 450° F. For ASTM D638 the Type I tensilebar crosshead speed was 50.8 mm/minute For ASTM D3763 the initialvelocity was about 3.2 meters/second; the maximum force range of the tupwas 17.9 kN; the sample support diameter (clamp inside diameter) is 76.0mm and the tup diameter is 12.8 mm. For UL94 the test used Section 850W(20 mm) Vertical Burn Test: V-0, V-1 or V-2.

TABLE 1 Copolyester TPA EG CHDM A 100 86 12 B 100 69 31 C 100 63.3 36.7

Examples 1 and 2, in Table 2, demonstrate the low haze of less than 6%and high light transmittance of 89% for copolyester B with 6 wt % PSPPP.In contrast, copolyester B with 10 wt % Spectarm FR1000 which contains acombination of a metal phosphinate and a melamine had a high haze of101% and low light transmittance of about 24%.

TABLE 2 ASTM D1003 Flame Light ASTM retardant Transmit- D523 Example wt% Copolyester Haze % tance % GLOSS 1 10 Copolyester B 101 23.7 55.2SPECTAR FR1000 2 6 Copolyester B 5.47 89.2 119.4 PSPPP

Examples 3 to 8, in Table 3, demonstrate that the glass transitiontemperature is maintained at about 78° C. for copolyester B with 2 to 10wt % PSPPP. Examples 3 to 6 all achieved a UL 94 rating of V-0 whileexamples 7 and 8 achieved a V-2 rating. The energy at max load wasmaintained above about 23 J for all examples (except for example 4 with8 wt % PSPPP). However, a higher load of 10 wt % PSPPP still maintainedan energy at max load value greater than 23 J.

TABLE 3 Instrumented Impact - ASTM D3763 Tensile Properties - ASTM D638Energy Yield Break Max Max Total Strength Elongation Strength ElongationModulus Load Load Sample # PSPP % (Mpa) at Yield % (Mpa) at Break %(Mpa) (KN) (J) 3 10 53.539 3.446 53.539 3.446 2267.788 3.24 23.82 4 826.449 1.263 26.449 1.263 2332.588 0.159 0.79 5 6 58.587 4.317 37.2445.03 2244.586 3.23 25.48 6 6 48.39 3.46 48.98 314.6 2082.72 3.9 31.6 7 456.481 4.376 24.751 7.904 2169.33 3.81 33.04 8 2 54.689 4.339 24.0757.956 2108.278 3.59 26.62 Instrumented Impact - UL94 ASTM D3763 GlassTotal Transition Burn Energy Temperature Time Sample # (J) Brittle % °C. (s) Rating Comments 3 34.32 40 79.52 0 94 V-0 (9) dripped, did notignite (1) did not drip 4 0.9 100 77.46 0 94 V-0 (10) dripped, did notignite 5 40.27 20 76.27 0 94 V-0 (10) dripped, did not ignite 6 46.6 2080.64 94 V-0 7 50.75 0 77.65 0.6 94 V-0 (7) dripped, did not ignite (3)dripped and did ignite 8 45.15 0 77.24 1.2 94 V-0 (5) dripped, did notignite (5) dripped and did ignite

Samples of copolyester A, copolyester B and copolyester C were meltcompounded with triphenyl phosphite (TPPi) at loadings from 0.25% to 3%.Copolyester A required at least 2% TPPi to achieve a UL 94 V-0 ratingand remain clear. Copolyester B required 3% TPPi to achieve a UL 94 V-0rating and remain clear. TPPi incorporated with copolyester C neverachieved a V-0 rating. Copolyester A and copolyester B, however, droppedin heat distortion temperature (ASTM 648) from 64° C. to 57° C. to 52°C. for copolyester A and from 65.25° C. to 49.8° C. for copolyester B.This drop in heat distortion temperature is very undesirable.

Examples 9-29: Flame Retarded Copolyester Blend with Tri-PhenylPhosphite

TABLE 4 Instrumented Impact ASTM 3763 0.125 HDT, 264 PSI Energy @MaxFacture Max target ASTM D648 Load Energy Load Thickness Example Polymer% TPPI T [° C.] % Brittle [ft-lb] [ft-lb] [lb] [in]  9 Copolyester AControl 0 64.65 0.00 24.20 38.29 895.36 0.13 10 Copolyester A + 0.25 wt% Triphenyl 0.25 phosphite 11 Copolyester A + 0.5 wt % Triphenyl 0.564.10 0.00 23.61 37.66 902.05 0.13 phosphite 12 Copolyester A + 0.75 wt% Triphenyl 0.75 phosphite 13 Copolyester A + 1 wt % Triphenyl 1 61.450.00 24.68 38.61 886.21 0.12 phosphite 13a Copolyester A + 1 wt %Triphenyl 0.5 63.75 0.00 26.78 39.51 938.99 0.12 phosphite 13bCopolyester A + 1 wt % Triphenyl 0.5 62.00 0.00 26.13 40.15 918.58 0.13phosphite 14 Copolyester A + 2 wt % Triphenyl 2 57.10 0.00 24.94 36.72921.75 0.13 phosphite 15 Copolyester A + 3 wt % Triphenyl 3 52.75 20.0022.25 36.31 848.22 0.13 phosphite 15a Copolyester A + 3 wt % Triphenyl 355.35 20.00 23.07 34.78 882.70 0.13 phosphite 16 Copolyester B Control 065.25 0.00 26.46 39.43 902.40 0.12 17 Copolyester B + 0.25 wt % 0.25Triphenyphosphite 18 Copolyester B + 0.5 wt % Tripheny 0.5 64.90 0.0027.17 41.46 906.97 0.13 phosphite 19 Copolyester B + 0.75 wt % 0.75Triphenyphosphite 20 Copolyester B + 1 wt % 1 60.75 0.00 26.29 41.16904.16 0.13 Triphenyphosphite 21 Copolyester B + 2 wt % 2 55.10 0.0026.14 38.15 922.80 0.13 Triphenyphosphite 22 Copolyester B + 3 wt % 349.80 0.00 25.41 37.73 916.12 0.13 Triphenyphosphite 23 Copolyester CControl 0 67.90 0.00 30.67 41.46 944.62 0.13 24 Copolyester C + 0.25 wt% Tripheny 0.25 phosphite 25 Copolyester C + 0.5 wt % Tripheny 0.5 64.600.00 33.40 44.76 958.69 0.13 phosphine 26 Copolyester C + 0.75 wt % 0.75Triphenyphosphite 27 Copolyester C + 1 wt % 1 64.35 20.00 32.37 44.00963.26 0.13 Triphenyphosphite 28 Copolyester C + 2 wt % 2 53.30 0.0027.34 39.96 912.25 0.13 Triphenyphosphite 29 Copolyester C + 3 wt % 352.25 0.00 24.86 36.80 864.40 0.13 Triphenyphosphite UL94-TESTED AS ISMAF TAF % OF Yes UL94 Example Polymer (sec) (sec) IC B2C Drip Rating  9Copolyester A Control 3.00 10.00 100% 0% 100% V-2 10 Copolyester A +0.25 wt % Triphenyl phosphite 1.00 5.00 100% 0% 100% V-2 11 CopolyesterA + 0.5 wt % Triphenyl phosphite 2.00 3.00 40% 0% 40% V-2 12 CopolyesterA + 0.75 wt % Triphenyl phosphite 0.00 0.00 100% 0% 0% V-0 13Copolyester A + 1 wt % Triphenyl phosphite 0.00 1.00 20% 0% 100% V-2 13aCopolyester A + 1 wt % Triphenyl phosphite 1.00 3.00 40% 0% 80% V-2 13bCopolyester A + 1 wt % Triphenyl phosphite 2.00 5.00 100% 0% 100% V-2 14Copolyester A + 2 wt % Triphenyl phosphite 0.00 0.00 0% 0% 60% V-0 15Copolyester A + 3 wt % Triphenyl phosphite 0.00 0.00 0% 0% 0% V-0 15aCopolyester A + 3 wt % Triphenyl phosphite 0.00 0.00 0% 0% 0% 0 16Copolyester B Control 5.00 21.00 100% 0% 100% V-2 17 Copolyester B +0.25 wt % Triphenyphosphite 1.00 4.00 100% 0% 100% V-2 18 CopolyesterB + 0.5 wt % Tripheny phosphite 1.00 3.00 100% 0% 100% V-2 19Copolyester B + 0.75 wt % Triphenyphosphite 0.00 0.00 100% 0% 100% V-220 Copolyester B + 1 wt % Triphenyphosphite 1.00 2.00 100% 0% 100% V-221 Copolyester B + 2 wt % Triphenyphosphite 1.00 1.00 100% 0% 100% V-222 Copolyester B + 3 wt % Triphenyphosphite 0.00 0.00 0% 0% 40% V-0 23Copolyester C Control 4.00 21.00 100% 0% 100% V-2 24 Copolyester C +0.25 wt % Tripheny phosphite 4.00 17.00 100% 0% 100% V-2 25 CopolyesterC + 0.5 wt % Tripheny phosphine 2.00 6.00 100% 0% 100% V-2 26Copolyester C + 0.75 wt % Triphenyphosphite 1.00 2.00 100% 0% 100% V-227 Copolyester C + 1 wt % Triphenyphosphite 1.00 2.00 100% 0% 100% V-228 Copolyester C + 2 wt % Triphenyphosphite 1.00 1.00 100% 0% 100% V-229 Copolyester C + 3 wt % Triphenyphosphite 1.00 1.00 100% 0% 100% V-2UL94-CONDITIONED MAF TAF % OF Yes UL94 Example Polymer (sec) (sec) ICB2C Drip Rating  9 Copolyester A Control 4 28 100% 0% 100% V-2 10Copolyester A + 0.25 wt % Triphenyl phosphite 5 23 100% 0% 100% V-2 11Copolyester A + 0.5 wt % Triphenyl phosphite 6 15 100% 0% 100% V-2 12Copolyester A + 0.75 wt % Triphenyl phosphite 1 1 100% 0% 100% V-2 13Copolyester A + 1 wt % Triphenyl phosphite 1 1 80% 0% 100% V-2 13aCopolyester A + 1 wt % Triphenyl phosphite 2 5 100% 0% 100% V-2 13bCopolyester A + 1 wt % Triphenyl phosphite 0 0 0% 0% 100% V-0 14Copolyester A + 2 wt % Triphenyl phosphite 0 0 0% 0% 100% V-0 15Copolyester A + 3 wt % Triphenyl phosphite 0 0 0% 0% 60% V-0 15aCopolyester A + 3 wt % Triphenyl phosphite 1 1 80% 0% 100% V-2 16Copolyester B Control 9 41 100% 0% 100% V-2 17 Copolyester B + 0.25 wt %Tripheny phosphite 5 17 100% 0% 100% V-2 18 Copolyester B + 0.5 wt %Tripheny phosphite 4 13 100% 0% 100% V-2 19 Copolyester B + 0.75 wt %Triphenyphosphite 0% 100% 20 Copolyester B + 1 wt % Triphenyphosphite 23 100% 0% 100% V-2 21 Copolyester B + 2 wt % Triphenyphosphite 1 1 100%0% 100% V-2 22 Copolyester B + 3 wt % Triphenyphosphite 0 0 0% 0% 100%V-0 23 Copolyester C Control 10 47 100% 0% 100% V-2 24 Copolyester C +0.25 wt % Tripheny phosphite 4 19 100% 0% 100% V-2 25 Copolyester C +0.5 wt % Tripheny phosphine 3 9 100% 0% 100% V-2 26 Copolyester C + 0.75wt % Triphenyphosphite 3 11 100% 0% 100% V-2 27 Copolyester C + 1 wt %Triphenyphosphite 3 5 100% 0% 100% V-2 28 Copolyester C + 2 wt %Triphenyphosphite 1 2 100% 0% 100% V-2 29 Copolyester C + 3 wt %Triphenyphosphite 0 0 60% 0% 100% V-2

Examples 30 to 32, in Tables 5, demonstrate that UL 94 V-0 ratings aremaintained for copolyester B with 5 to 8 wt % of PSPPP. The energy atmax load was maintained above about 15 J for all Examples in this group(except for example 32 with 8 wt % PSPPP). Examples 30 to 32 allachieved a UL 94 V-0 before and after aging samples at 70° C. for 168hours.

TABLE 5 Instrumented Impact - ASTM D3763 Energy Max PSPPP Max Load LoadTotal Energy Example Concentration % (kN) (J) (J) Break Type 30 5 3.2821.79 30.93 60% B 31 6 2.79 16.19 20.2 80% B 32 8 0.81 1.05 1.35 100% B Total After- Reps Total Flame Igniting Max Flame & Number PSPPP (t1 +Cotton Total Flame Glow Burn to After-Flame After-Flame ExampleConcentration % t2) (DIC) Classification Drips Time Time Clamp Time (t1)Time (t2) UL 94 Results Before Aging 30 5 0 0 V-0 10 0 0 0 0, 0, 0, 0, 00, 0, 0, 0, 0 31 6 0 0 V-0 10 0 0 0 0, 0, 0, 0, 0 0, 0, 0, 0, 0 32 8 0 0V-0 10 0 0 0 0, 0, 0, 0, 0 0, 0, 0, 0, 0 UL 94 Results After Aging 30 511 0 V-0 10 2 5 0 2, 1, 1, 1, 1 1, 1, 1, 1, 1 31 6 11 0 V-0 10 2 5 0 2,1, 1, 1, 1 1, 1, 1, 1, 1 32 8 10 0 V-0 10 1 5 0 1, 1, 1, 1, 1 1, 1, 1,1, 1

Examples 33 to 36, in Table 6, demonstrate that clarity is maintainedfor compositions of copolyester B with various concentrations of PSPPP.Examples 33 to 35 with 5 wt % to 8 wt % of PSPPP all achieved a high %of light transmissions with low haze values. Example 36 with no PSPPPhad high light transmission and low haze.

TABLE 6 PSPPP Light Transmission % Example Concentration % (ASTM D1003)Haze 33 5 87.6 0.79 34 6 87.1 0.86 35 8 85.6 0.89 36 0 90.80 0.62

Examples 37 to 40, in Table 7, demonstrate that UL-94 V-2 and V-0results can be achieved for copolyester B at 15 mil thickness. Example37 failed to achieve a rating at 2 wt % PSPPP. Examples 38 and 39, at 3wt % and 4 wt % PSPPP achieved a V-2 rating. Example 40 achieved a V-0rating at 5 wt % PSPPP.

TABLE 7 UL 94 PSPPP Reps Igniting Total After- Example Concentration %Cotton (DIC) Flame (t1 + t2) Rating 37 2 0 5 FAIL 38 3 4 10 V-2 39 4 511 V-2 40 5 0 15 V-0

Examples 41 to 44, in Table 8, demonstrate that UL-94 VTM-2 and VTM-0ratings can be achieved for copolyester B at a 5 mil thickness. Examples41 and 42, with 2 wt % and 3 wt % PSPPP achieved a UL-94 VTM-2 rating.Examples 43 and 44, with 4 and 5 wt % of PSPPP achieved a UL-94 VTM-0rating. Generally, when the thickness of the material decreases, it ismore difficult to maintain flammability performance. However, for verythin films with 5 mil thickness in Examples 43 and 44 VTM-0 rating wereachieved and Examples 41 and 42 achieved VTM-2 ratings.

TABLE 8 UL 94 VTM Total Reps Total After- Igniting Max Flame NumberAfter- After- Wt % Flame Cotton Total Flame & Glow Burn to Flame FlameExample PSPPP (t1 + t2) (DIC) Rating Drips Time Time Clamp Time (t1)Time (t2) 41 2 17 4 VTM-2 7 4 7 0 1, 2, 1, 4, 2 1, 1, 1, 2, 2 42 3 14 3VTM-2 7 3 6 0 2, 1, 3, 1, 1 1, 2, 1, 1, 1 43 4 10 0 VTM-0 4 1 5 0 1, 1,1, 1, 1 1, 1, 1, 1, 1 44 5 10 0 VTM-0 6 1 5 0 1, 1, 1, 1, 1 1, 1, 1, 1,1

The invention has been described in detail with reference to theembodiments disclosed herein, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A copolyester composition comprising: (a) from greater thanabout 90 to about 98 wt % of the copolyester comprising (i) a diacidcomponent comprising from 70 to 100 mole % residues of terephthalicacid, from 0 to 30 mole % residues of a modifying aromatic diacid havingfrom 8 to 12 carbon atoms, and from 0 to 10 mole % residues of analiphatic dicarboxylic acid; and (ii) a glycol component comprising from1 to 65 mole % cyclohexanedimethanol residues and from 35 to 99 mole %of a modifying glycol having 2 to 20 carbon atoms; (b) from about 2 toabout 10 wt % of a flame retardant comprising a polymer comprising asulfonyl moiety and a phenyl phosphonate moiety, wherein the copolyestercomposition has a UL 94 V-0 rating, wherein the energy at maximum loadis greater than about 15 Joules according to ASTM D3763; wherein thecopolyester composition has less than about 10% haze according to ASTMD1003, wherein the wt % is based on the weight of the copolyester,wherein the total mole % of the dicarboxylic acid component is 100 mole% and the total mole % of the glycol component is 100 mole %.
 2. Thecopolyester composition according to claim 1 wherein the copolyestercomposition further comprises a drip suppressant or an impact modifieror mixtures thereof.
 3. A method of making a copolyester composition,the method comprising blending: (a) from greater than about 90 to about98 wt % of the copolyester comprising (i) a diacid component comprisingfrom 70 to 100 mole % residues of terephthalic acid, from 0 to 30 mole %residues of a modifying aromatic diacid having from 8 to 12 carbonatoms, and from 0 to 10 mole % residues of an aliphatic dicarboxylicacid; and (ii) a glycol component comprising from 1 to 65 mole %cyclohexanedimethanol residues and from 35 to 99 mole % of a modifyingglycol having 2 to 20 carbon atoms; (b) from about 2 to about 10 wt % ofa flame retardant comprising a polymer comprising a sulfonyl moiety anda phenyl phosphonate moiety, wherein the copolyester composition has aUL 94 V-0 rating, wherein the energy at maximum load is greater thanabout 15 Joules according to ASTM D3763; wherein the copolyestercomposition has less than about 10% haze according to ASTM D1003,wherein the wt % is based on the weight of the copolyester, wherein thetotal mole % of the dicarboxylic acid component is 100 mole % and thetotal mole % of the glycol component is 100 mole %.
 4. The method ofmaking a copolyester composition according to claim 3, wherein (a) thecopolyester is from about 93 to about 95 wt %; and (b) the flameretardant from about 5 to about 7 wt %, wherein the copolyestercomposition has a UL 94 V-0 rating, and wherein the energy at maximumload is greater than about 23 Joules according to ASTM D3763.
 5. Themethod of making a copolyester composition according to claim 3, wherein(a) the copolyester is from about 90 to about 95 wt %; and (b) the flameretardant from about 5 to about 10 wt %, wherein the copolyestercomposition has a UL 94 V-0 rating, and wherein the energy at maximumload is greater than about 23 Joules according to ASTM D3763.
 6. Themethod of making a copolyester composition according to claim 3, whereinthe copolyester composition has less than about 5% haze.
 7. The methodof making a copolyester composition according to claim 3, wherein theflame retardant comprises polysulfonyldiphenylene phenyl phosphonate. 8.The method of making a copolyester composition according to claim 3,wherein the blending comprises at least one of twin screw compounding,two-rotor continuous compounding, Banbury® batch mixer or a combinationthereof.
 9. An article comprising a copolyester composition comprising:(a) from greater than about 90 to about 98 wt % of the copolyestercomprising (i) a diacid component comprising from 70 to 100 mole %residues of terephthalic acid, from 0 to 30 mole % residues of amodifying aromatic diacid having from 8 to 12 carbon atoms, and from 0to 10 mole % residues of an aliphatic dicarboxylic acid; and (ii) aglycol component comprising from 1 to 65 mole % cyclohexanedimethanolresidues and from 35 to 99 mole % of a modifying glycol having 2 to 20carbon atoms; b) from about 2 to about 10 wt % of a flame retardantcomprising a polymer comprising a sulfonyl moiety and a phenylphosphonate moiety, wherein the copolyester composition has a UL 94 V-0rating, wherein the energy at maximum load is greater than about 15Joules according to ASTM D3763; wherein the copolyester composition hasless than about 10% haze according to ASTM D1003, wherein the wt % isbased on the weight of the copolyester, wherein the total mole % of thedicarboxylic acid component is 100 mole % and the total mole % of theglycol component is 100 mole %.
 10. The copolyester compositionaccording to claim 1 or 9, wherein the copolyester compositioncomprises: (a) from 90 to 96 wt % of the copolyester; and b) from 4 to10 wt % of the flame retardant, wherein the copolyester composition hasa UL 94 V-0 rating.
 11. The copolyester composition according to claim 1or 9, wherein the copolyester composition comprises: (a) from 92 to 98wt % of the copolyester; and b) from 2 to 8 wt % of the flame retardant,wherein the copolyester composition has a UL 94 V-0 rating.
 12. Thecopolyester composition according to claim 1 or 9, wherein thecopolyester composition comprises: (a) from 92 to 96 wt % of thecopolyester; and b) from 4 to 8 wt % of the flame retardant, wherein thecopolyester composition has a UL 94 V-0 rating.
 13. The copolyestercomposition according to claim 1 or 9, wherein the copolyestercomposition comprises: (a) from about 93 to about 98 wt % of thecopolyester; and b) from about 5 to about 7 wt % of the flame retardant,wherein the copolyester composition has a UL 94 V-0 rating.
 14. Thecopolyester composition according to claim 1 or 9, wherein the flameretardant comprises polysulfonyldiphenylene phenyl phosphonate.
 15. Thecopolyester composition according to claim 1 or 9, wherein thecopolyester composition has less than about 5% haze.
 16. The copolyestercomposition according to claim 1 or 9, wherein the energy at maximumload is greater than about 23 Joules according to ASTM D3763.
 17. Thearticle according to claim 9, wherein the article is produced byextrusion, extrusion blow molding, injection molding, blown film processor calendering.
 18. The article according to claim 17, wherein thearticle is a film, sheet or profile.
 19. A film comprising a copolyestercomposition comprising: (a) from greater than about 90 to about 98 wt %of the copolyester comprising (i) a diacid component comprising from 70to 100 mole % residues of terephthalic acid, from 0 to 30 mole %residues of a modifying aromatic diacid having from 8 to 12 carbonatoms, and from 0 to 10 mole % residues of an aliphatic dicarboxylicacid; and (ii) a glycol component comprising from 1 to 65 mole %cyclohexanedimethanol residues and from 35 to 99 mole % of a modifyingglycol having 2 to 20 carbon atoms; (b) from about 2 to about 10 wt % ofa flame retardant comprising a polymer comprising a sulfonyl moiety anda phenyl phosphonate moiety, wherein the film has a thickness of 1-10mils and has a VTM-0 or VTM-2 rating, and wherein the film has less thanabout 10% haze according to ASTM D1003, wherein the wt % is based on theweight of the copolyester, wherein the total mole % of the dicarboxylicacid component is 100 mole % and the total mole % of the glycolcomponent is 100 mole %.